83004-45-9Relevant academic research and scientific papers
A NEW SYNTHESIS OF ALKYL FLUORIDES
Purrington, Suzanne T.,Pittman, James H.
, p. 6851 - 6852 (1988)
Reduction of α-fluorosulfides with sodium in alcohol results in the formation of fluoroalkanes.
Chemoselective Homologation-Deoxygenation Strategy Enabling the Direct Conversion of Carbonyls into (n+1)-Halomethyl-Alkanes
Citarella, Andrea,Holzer, Wolfgang,Ielo, Laura,Langer, Thierry,Miele, Margherita,Pace, Vittorio,Urban, Ernst,Zehl, Martin
supporting information, p. 7629 - 7634 (2020/10/12)
The sequential installation of a carbenoid and a hydride into a carbonyl, furnishing halomethyl alkyl derivatives, is reported. Despite the employment of carbenoids as nucleophiles in reactions with carbon-centered electrophiles, sp3-type alkyl halides remain elusive materials for selective one-carbon homologations. Our tactic levers on using carbonyls as starting materials and enables uniformly high yields and chemocontrol. The tactic is flexible and is not limited to carbenoids. Also, diverse carbanion-like species can act as nucleophiles, thus making it of general applicability.
Replecement of the carboxylic acid function with fluorine
Patrick, Timothy B.,Johri, Kamalesh K.,White, David H.,Bertrand, William S.,Mokhtar, Rodziah,et al.
, p. 138 - 141 (2007/10/02)
Replacement of a carbonyl function by fluorine, fluorodecarboxylation, is a new process that can be accomplished by the reaction of alkanoic acids with xenon difluoride.Primary, tertiary, and benzylic acids perform best in the reaction, which is conducted at room temperature in methylene chloride or chloroform solution.A reaction mechanism is proposed in which the acid is initially converted to a fluoroxenon ester, RCO2XeF.The esters of the primary and secondary acids react by nucleophilic displacement by fluoride, as evidenced by incorporation of 18F- and no reactions common to free radicals or carbocations.The esters of the tertiary and benzylic acids react by converting to free radicals that can be further oxidized to carbocations.Thus incorporation of 18F- and racemization are observed with α-methoxy-α-trifluoromethylphenylacetic acid.Hydroxyl and amino functions inhibit the reaction.Aromatic and vinylic acids do not react.
The reinvestigation of the kinetics of the reactions of fluorodi(4-nitrophenyl)ethanes with sodium methoxide in methanol
Leffek, Kenneth T.,Schroeder, Grzegorz
, p. 1696 - 1701 (2007/10/02)
The procedure previously described for the preparation of 1-fluoro-2,2-di(4-nitrophenyl)ethane actually yields 1,1,2-tri(4-nitrophenyl)ethane.Fluoro-2,2-di(4-nitrophenyl)ethane has been prepared and rate constants, isotope effects, and activation parameters for the β-elimination reaction with methoxide ion in methanol are reported.These parameters indicate a concerted E2 mechanism, with a fairly symmetrical transition state.The subsequent dimerization reaction of the olefin product to yield 1,1,3,3-tetra(4-nitrophenyl)butene-1 is described.The reaction of 1,1,1-trifluoro-2,2-di(4-nitrophenyl)ethane with methoxide ion in methanol has been reinvestigated and the reaction on the first product 1,1-difluoro-2,2-di(4-nitrophenyl)ethylene with excess methoxide, to give di(4-nitrophenyl)ketene dimethylacetal in a multistep reaction, is reported.
